Accelerator compound and process of preparing same



E1 yield .a rubber.

p Patented Man I 1cm eem ermn img qcm F PREPARI' l new i This i vention" relates to '1 a {new mass of l productsjand to thefproce'ssofprepari'ngthe 7 same. More specifically it relates toflavclass V bfocompounds resulting-"from'the interaction T1 5 of an aldehyde,faprimary amineeandfcarbon disulphidey the, production of novel compounds of val liable characteristics; In particular, it"is' the 1 objectof thefinventionito producecompounds especially adapted; to, accelerateithe' vulcani tuition of "rubber and 'whi rchrwi lywh i m V r ployed as accelerators; reduce' the l time :re fox-satisfactory vulcanizationyand, I

product of superior quality I quired aridrdurability.) 1:: v

--.j-'Ihis application iis inltlie-nature-lof acon} 7 tinuation, in part, of .my application Serial -No.-34,732, filed June:aaeasyraem 1,732,532

' d ted October 2251929 which covers products 7 a. resultingafromf the -interaction};of an aldehyde, asprimary amine, andfcarbondisuL phide and the.employmentoffthese products as"vulcanizationaccelerators; 5"

' 54 Ilia'venow discovered that if the-carbon bisulphide is causedto react withcthexaniine first and 'tliei'resulting product them'caused I to -reactrfwithl the aldehyde, ,thatfproducts I I f particularly valuable fo'rflu'se' as accelerators arefobtained; Also;'l 'have' discoyeredthat? those aaldehydes ;i"containing'fafplurality" f carbon atoms are best adapted forfjlthe pro-. lduction'of accelerators of thi's typeand'that,

-if'lcertain ratios of-theflthree'-coinponents,'- which ratios were uot;specifically disclosed V in the previous oapplication;:.,aresemployed,

' products of Very unusual activityasaccelerating agents result. -*sParticularlyyl'have discovered that the" useoftwo, 'three, fouror l-fThe inventionthas v a e I a p t p x This dithio carba mate; is heatedjunder pressure with two or more moles ofrp ar aldehydejl 55 r "b N wfiitsgormfimsoizotu,iEasEm-Assmuoal rofln i,"nuafieoim I 3 9 Q Q L M G DELAWARE; abonrommiort or rnm-y; "WARE? pounds resulting fare d I 1' fi a'a d tease; alad is formedz-f v 1 Y the addition compoundja; dithio carbamate;

to giye', most' prob ably acondensation prod; uct with tl e elimination o f ater.

, The preparation of the, new accelerators L may belbest d'isclosed'by the presentatlonof a; number "of examples embodyingthe inven;

tion; It is tobe understood that these exam plesjare purely illustrativeand that the conditions,; "reagents and proportions; therein 1 specified are susceptible of variation. ;;T he

exalriples follow:

Emample" .'1."To twofhu'ndred 'andfifte'en poundshofzmelted paratoluidine', onehundred: pounds ofcarbon bisulphi de' is slowlywadded under a refluxi'condenserq; Four hundred and 1 I fifty'pounds ofjbutyraldehyde isslowlyi'adde'd andjthe product heated under pressure for I "threeihours at;'C. The Water is'separated andth e product, dried in, vacuum; Ina stock of'onehundredpartsof smoked s heet ,i three j parts otz iiic oxide thr'eeiand'a 'half parts 7 a of isulphurfa'nd 0.375 "pa-11s" of? accelerator, 7 I a goodfcure'awas obtained in thirty-gminutesi I at twenty five pounds steam-pressuregwj'The 1,59 quantities employed in this example, corre- Q spond {to 3.1 'moles of aldehyde; 1 mole of 1 amine aud .66 moleof carbon bisulphi'de. =1: e ,Eacam-ple 2.-ToltWo hundred pounds {of iii] ' even five moles'of analdehyde-fwitbone mole 1 1 of: amine givescompounds ofremarkable acv *tivity. j, The amines and aldeliy des used *may be;eitherialiphatic 'or aromatic; although :in theipreferred embodimentsofmiy invention If employ aliphatic aldehyde-s 5 The com-- of, carbon bisulfideq" The product is cooled i a nd mixed until the reaction is complete. One

added :bclow-the, surface, cooling tlie mixture 5 anilineare slowly added one ihundre d pounds 13, i

thousand pounds@of'heptaldehyde are then} I is heated under pressure at 125 C. for three hours. The resulting compound is purified by distilling ofi anyunreacted volatile'materials under vacuum. This product, when tested in a percentage of'0.5, in a stoclccontaining one hundred parts ofsmolred sheet,

five parts of zinc oxide, and three parts of sulphur,'gave a good cure in thirty minutes at twenty-five pounds steam pressure. The quantities employed inthis example correspond'to eulmoles of aldehyde, lrnole of amine and .61 moleof carbon bisulphide;

E'amnple 3.One hundred pounds oficarboil .bisu-lphid'eare slowly added, under reflux,

to one hundred 'fifty'pounds of-bu'tylamine, WhlClllllS previously been cooled to 0 C.-

After the addition is V complete six hundred pounds of butyraldehyde are rapidly added.

. The autoclave is closed and the mixture heated to 110 C. for two hours, after'whlch any unreacted Volatile "constituents are i-e.

moved under vacuum. This'product. when tested in a percentage of 0.375, in a stockcontamlng one hundred parts of smoked sheet,

five parts of zinc oxide, and three partsof sulphur, 'gaveta' good cure; 1n twenty-five minutes at twenty five pounds steam pressure.

The quantities employed in this exaimplecor respond to 4.1 moles of aldehvdeil mole-of amine'and camels of carbonbisulphide,

While I have mentioned foripurposes of illustration definite quantitiesofthereacting components and certain specific temperatures and times of reaction, and in general have given exact conditions under which my improved compounds may be made, I, of course,

7 may be employed.

do not limit myself to these specific proportlons or conditions.) These illustrative con;

'ditions and methods ofefi'ecting the interaction andcombination of the ingredients may obviously be varied without departing from' my invention. In certain cases I may use more than-one aldehyde andlmay, of course,

use other aldehydes than those specified-in the examples, alsomorethan one amine-or a mixture of aromatlc and aliphatic amines may be used. As little as one half a mole of carbon disulphide'for each mole of amine In theclaims whereI amines as the homologues of aniline. W'here Ispecifyrubber? l inte'ndlto cover all the botanical varieties of caoutchouc, whichin- 'clude, Hevea, balata, gutta1percha, etc, and recognized substitutes therefor The vulcanization of the rubber compounds resulting from the employment of the new accelerator products is effected in less than'the time normally required and the resulting rubber is of superior quality. '5

II claim?" r 1 1. The product obtained by causing carbon bis ulphide to react with a primary aromatic amine to form a dithio carbamate andsubspecify an amine, I lntend to cover, also, the substituted primary sequently causing this reaction product to further react with an aldehyde.

' 2. The product obtained by causing carbon bisulphide to react with a primary aromatic amine to form an addition product and subsequently causing this product to further're act with an aldehyde. V

3. The product obtained by causing carbon bisulph ide to react with a primary aromatic aminejto form an addition product and subsequently causing'this product to further react with an aliphatic aldehyde.

. 4. The product obtainedby causing carbon bisulphideito react urith primary aromatic amine to form an additionproduct and,sub-

sequently-causing this product to further re- ;act. with an aliphatic aldehyde containing a plurality of carbon, atoms. V V ,5. .Theproductobta-ined by causing carbon bisulphide to react with a, primary aromatic amine tjo form an addition product andsubsequently causingthisproduct to further react with butyraldehydep 6. The productobtained by causing carbon bisulphide to react' with anilineto form an I addition product and subsequentlypausing "this Product to further eactwith butyraldeydew l f7l The product set forth-Tin claim 1, in which two 'to four moles of aldehyde are employed for every mole of amine;

8. The product set forthin claim-1, in

which between three and five moles of aldehyde are employed for every mole of amine. 9. The process of producing arcomp ound adapted for use as a rubber vulcanization accelerator, which comprises causing an aldehyde to react on the addition product of 'a adapted for use as arubbervulcanization accelerator, which comprises causing an aliphaticaldehyde gto reactionthe addition product. of'a primary aromatic amine and V carbon bisulphide.

I 12. The process of producing a comp'oun'd adapted for use as .a rubber vulcanization accelerator, which comprises causing an'aliphat-i aldehyde containing a plurality of carbon atomsfto react onthe additionprodnot of a primary aromatic amine and carbon bisulphide. i 13.. The process of producing a compound adapted for use as a .rubber vulcanization accelerator, which comprises causing .buty'raldehyde to react on the addition product of asprimary aromaticami'ne and carbon bisulphide. I

l J The processpfdp' a i g a compound: t I v ,adaptedsfor use asrubberv V1110anizationivl 4 "Iacceleraflcor;whichcompriss causing."butygy 1 v v aldehyde to feact on theaddition'producfioffi" i V aniline and carbon bisulphide.

' 15,.[The process set fdi'thlinxclaim Qwhere-I ingtwo tofour moles of "aldehyde areilem f I ployed for every mole ofaminet H {1} 16. Theprbcess set forth 'ini claim 9.- where- 10 in'betweenthreeand fivemol'es of aldehyde 'four 'mol'es of butyraldehyde toireact onthefl.

In testimonywhereofgl aflix I areemployedIforevetyimole"of jamine. I '17. The process of producing a; compqund r adapt-ed for use as'a rubbenvulcanization ac celrator, which comprises causing two "to 

